JPH10177229A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and its processing method capable of enhancing scratch resistance without deteriorating sensitivity and a gamma value. SOLUTION: The silver halide photographic sensitive material is provided on a support with hydrophilic colloidal layers including at least one photosensitive silver halide emulsion layer and these hydrophilic colloidal layers contain a hydrazine compound or its combination with a nucleating accelerator and the outer hydrophilic colloidal layer of at least 2 hydrophilic colloidal layers located on the outermost silver halide emulsion layers contains as a matting agent at least one kind of organic polymer having an average particle diameter of 1.0-10μm and at least one kind of inorganic powder having an average particle diameter of 1.0-100μm, and the hydrophilic colloidal layer in the inside contains a polymer latex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a high-sensitivity, high-contrast silver halide photographic light-sensitive material for printing plate making and a processing method thereof.

[0002]

2. Description of the Related Art A photographic film has many opportunities to come into contact with the film surface in a transport system during a manufacturing process. Furthermore, there are many opportunities in the exposure and development processing. For example, in the case of an output photosensitive material for printing plate making, a silver halide photographic photosensitive material (hereinafter simply referred to as a photosensitive material) is automatically loaded and exposed after being loaded into an imagesetter. Processed and dried by an automatic processor.

In the course of these transportations, the photosensitive material comes into contact with various parts, and therefore, there is a problem that blackening pressure called abrasion failure easily occurs on the film surface.

In particular, a high-sensitivity, high-contrast output photosensitive material using a hydrazine compound has a problem that blackening pressure is more likely to occur than other photosensitive materials, and improvement thereof has been desired.

A number of proposals have been made on techniques for improving the pressure resistance of photosensitive materials, but they are not sufficient to prevent blackening pressure without deteriorating photographic performance of high sensitivity and high contrast. Needed development.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for printing plate making which is excellent in scratch resistance, and a further object is to provide a high-sensitivity silver halide photographic material using a hydrazine compound. An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, ultra-high contrast photographic performance, and excellent scratch resistance.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains a hydrazine compound; In addition, the outermost layer of the silver halide emulsion layer has at least two hydrophilic colloid layers, and the outer hydrophilic colloid layer contains at least an organic polymer particle having an average particle size of 1.0 to 10 μm as a matting agent. A silver halide photographic light-sensitive material comprising a matting agent comprising one kind and at least one kind of inorganic particles having an average particle size of 1.0 to 100 [mu] m, and containing a polymer latex in an inner hydrophilic colloid layer. material.

(2) In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, a hydrazine compound and a compound represented by the following general formula are contained in the hydrophilic colloid layer. [Na], [Nb]
Or at least one of the compounds represented by [Nc], and the outermost layer of the silver halide emulsion layer has at least 2
Layer having a hydrophilic colloid layer, of which the outer hydrophilic colloid layer has a mean particle size of 1.0 to 10 μm as a matting agent.
m and at least one kind of organic polymer particles having an average particle diameter of 1.
A silver halide photographic light-sensitive material comprising a matting agent comprising at least one inorganic particle having a particle size of 0 to 100 [mu] m, and a polymer latex in an inner hydrophilic colloid layer.

[0010]

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(In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group, and R ₁ , R ₂ and R ₃ may form a ring.

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group.

R ₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, but Ar and R ₄ may be connected to each other by a linking group to form a ring.

In the general formula [Nc], Q represents an N or P atom, and R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substitutable group. L represents an m-valent organic group. R ₅ to R ₇ and L
May have a plurality of groups bonded to each other to form a ring. m represents an integer of 1 to 5. X ^n- represents an n-valent anion, and n represents an integer of 1 to 5. X ^n- may be linked to L. (3) The average particle diameter of the matting agent which is an inorganic particle is 3 to 100.
The silver halide photographic material as described in (1) or (2) above,

(4) The silver halide photograph as described in any one of (1) to (3) above, wherein the hydrophilic colloid layer including the silver halide emulsion layer contains colloidal silica. Photosensitive material.

(5) The silver halide photographic light-sensitive material as described in any one of (1) to (4) above, wherein the outermost layer of the silver halide emulsion layer contains at least one kind of slip agent. material.

Hereinafter, the present invention will be described in detail.

The silver halide photographic material of the present invention has a hydrophilic colloid layer including a photosensitive silver halide emulsion layer. The term "hydrophilic colloid layer" as used herein refers to all layers constituting the silver halide photographic material, and includes, for example, a silver halide emulsion layer, a protective layer, an intermediate layer, an antistatic layer, a dye layer and the like.

The silver halide photographic light-sensitive material of the present invention contains a hydrazine compound in the hydrophilic colloid layer, and comprises at least two hydrophilic colloid layers as the outermost layer of the silver halide emulsion layer, that is, as a protective layer. Have. A matting agent comprising organic polymer particles and inorganic particles is contained as a matting agent in the outer hydrophilic colloid layer (in the present invention, referred to as the emulsion protective layer 2 composition) of the protective layer, and the inner hydrophilic colloid layer ( In the present invention, the polymer latex is contained in the emulsion protective layer 1 composition).

In the present invention, as the inorganic particles, for example, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, British Patent No. 1,
173, 181 and carbonates such as cadmium and zinc.

Examples of the organic polymer particles in the present invention include starch described in US Pat. No. 2,322,037, Belgian Patent No. 625,451, and British Patent No. 981,1.
98, polyvinyl alcohol described in JP-B-44-3643, polystyrene or polymethyl methacrylate described in U.S. Pat. No. 330,158, polyacrylonitrile described in 3,079,257, and 3rd. 022,169 or copolymers thereof.

These matting agents include those subjected to a surface treatment. Examples of the surface treatment include gelatin, a binder for gelatin, alcohols, halogens, oxygen, amine compounds, silane coupling agents, and surfactants. , A crosslinkable resin, a saccharide or other organic compound, an organic polymer, or the like may be used.

In the present invention, the above-mentioned inorganic particles preferably have an average particle size of 1 to 100 μm, and more preferably have an average particle size of 1 to 50 μm
m is preferred. The amount may in 0.1-100 mg / m ^2, more preferably from 3 to 100 mg / m ^2. At the time of addition, a solution appropriately diluted with water or a hydrophilic solvent may be added to the coating solution.

The average particle size of the organic polymer particles is 1 to 10 μm.
Is preferable, and the average particle size is particularly preferably 1.5 to 8 μm.
The addition amount may be 0.1 to 100 mg / m ² , and particularly preferably 1 to 100 mg / m ² . In particular, it preferably contains 1 to 100 mg / m ² of particles having an average particle diameter of 3 μm or more, and 1 to 100 mg / m ² of particles having an average particle diameter of 5 μm or more.
It is particularly preferred to contain m ² .

[0025] The most preferable amount of the inorganic particles is 3
-100 mg / m ² , organic polymer particles 3-100 m
g / m ² in the uppermost protective layer.

The above combinations can be used in any proportion, but the total amount is preferably 3 to 150 mg / m ² . . In the present invention, the colloidal silica used in the hydrophilic colloid layer including the silver halide emulsion layer has an average particle size of 0.01 to 1 μm, preferably 0.01 to 1 μm.
0.5 μm. The amount used is 0.1-2000mg / m
² , and particularly preferably 10 to 1000 mg / m ² .

The main component of the colloidal silica is silicon dioxide, and may contain alumina or sodium aluminate as a minor component. These colloidal silicas may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia as a stabilizer.

Specific examples of these colloidal silicas include, for example, E.C. I. Du Pont de Nemovs
Ludox AS, LS from & Co (USA)
TM, HS, etc., Snowtex 20, 30, C, O, etc. from Nissan Chemical Co., Ltd., Syton zoo from Monsanto Co, Nalcoag-1060, Nalcoag-ID from Nalco Chem Co.
It is commercially available under trade names such as 21 to 64, and these can be easily obtained.

The colloidal silica addition layer is preferably a silver halide emulsion layer and / or a hydrophilic colloid layer outside the silver halide emulsion layer.

In the present invention, the outermost protective layer includes
A slip agent is included. As the slipping agent, any known slipping agent can be used. For example, a polysiloxy acid wax or silicone oil is advantageously used.

The amount of these used is 0.1 to 2000
mg / m ² , and particularly preferably 1 to 100 mg / m ² . The timing of addition may be any time, and may be added separately or in combination with the above matting agent. The slip agent may be appropriately diluted in water or a hydrophilic solvent and added to the coating solution.

Next, a polymer latex is contained in the composition of the emulsion protective layer 1 provided below the uppermost protective layer among the protective layers in the present invention.

As the polymer latex to be used,
There is no particular limitation, for example, US Pat.
No. 72,166, No. 3,325,286, No. 3,
No. 411,911, No. 3,311,912, No. 3,525,620, Research Disclosure (Research Disclosure Magazine No. 1)
9551) (July 1980) and the like, and hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters, and styrene can be used.

The polymer latex preferably used in the present invention includes a homopolymer of methalkyl acrylate such as methyl methacrylate and ethyl methacrylate, a homopolymer of styrene, or a methalkyl acrylate, styrene and acrylic acid, N-methylol acrylamide, glycidol. Copolymer with methacrylate, etc., homopolymer of alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or copolymer of alkyl acrylate with acrylic acid, N-methylol acrylamide (preferably copolymer of acrylic acid, etc.) Component is up to 30% by weight), butadiene homopolymer or copolymer of butadiene with one or more of styrene, butoxymethylacrylamide, acrylic acid, vinylidene-methyl chloride Acrylate - like terpolymer acrylic acid. Specific examples of the polymer latex that can be used in the present invention are shown below.

These polymer latexes have a Tg
Is particularly preferably 20 ° C. or lower, but the Tg of a polymer latex composed of a copolymer of two or more components can be easily adjusted by changing the component ratio. Represents a polymer latex having an arbitrary composition ratio of the polymer latex composed of the constituent components. Of course, the specific examples of the polymer latex shown here are only one example of the polymer latex that can be used, and the constituent components (not only the composition ratio) of the polymer latex used in the present invention are not limited to these specific examples. Needless to say.

Specific examples of the polymer latex used in the present invention are shown below.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The preferred range of the average particle size of the polymer latex used in the present invention is from 0.005 to 1 μm, especially from 0.
It is preferably from 02 to 0.1 μm.

The preferable addition amount of the polymer latex to the silver halide emulsion layer is 70% or more based on gelatin. Particularly preferably, it is 70 to 200% or more.
Gelatin amount of preferred emulsion layer is preferably 3 g / m ² or less, 2.5 g / m ² or less is particularly preferred.

In the present invention, Japanese Patent Application Laid-Open No. 5-66
For example, a gelatin latex stabilized polymer latex disclosed in U.S. Pat. No. 512 may be used.

The ordinary latex is aqueous-dispersed by a surfactant, but the polymer latex is characterized in that the surface and / or the interior is dispersion-stabilized by gelatin. The polymer constituting the latex and the gelatin may have some kind of bond. in this case,
The polymer and gelatin may be directly bonded, or may be bonded via a crosslinking agent. For this reason, the monomers constituting the latex include carboxyl groups, amino groups,
It is desirable to include those having a reactive group such as an amide group, an epoxy group, a hydroxyl group, an aldehyde group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group, and an unsaturated carbon bond. When a cross-linking agent is used, the one used as a normal gelatin cross-linking agent can be used. For example, aldehyde type,
Glycol-based, triazine-based, epoxy-based, vinylsulfone-based, oxazoline-based, methacryl-based, and acrylic-based crosslinking agents can be used.

The latex stabilized with gelatin is
At least part of the polymerization reaction of the polymer is performed in a solvent containing at least gelatin.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention contains a hydrazine compound. Preferred examples of the hydrazine compound include compounds represented by the following general formula [H].

[0050]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents an R ₂ — group or an iminomethylene group, n represents an integer of 1 or 2, and both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino A carbamoyl group or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0053]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and are preferably both hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, an carbamoyl group, or an oxycarbonyl group. Most preferred R ² includes a —COOR ₃ group and —CON (R ₄ )
(R ₅₎ groups (R ₃ represents an alkynyl group or a saturated heterocyclic group, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

A more preferred R ² is an alkyl group. R ² is preferably a substituted alkyl group, more preferably a substituted methyl group, and most preferably a substituted methyl group. Specific examples of the substituent include alkoxy, aryloxy, heterocyclic oxy, mercapto,
Alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, heterocyclic sulfonyl, acyl, cyano, chlorine, bromine, fluorine, nitro, alkoxycarbonyl, aryloxycarbonyl, carboxyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, amino, alkyl Examples include groups such as amino, arylamino, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, acyloxy, alkylaminocarbonyloxy, arylaminocarbonyloxy, sulfo, sulfamoyl, arylsulfamoyl, and alkylsulfamoyl. Preferred are chlorine, bromine and fluorine, and more preferred is fluorine.

In the hydrophilic colloid layer of the light-sensitive material of the present invention, a compound represented by the following general formula [1] can be preferably used as a hydrazine compound.

[0063]

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In the formula, R ¹ represents a monovalent substituent. A ¹ , A
² represents a hydrogen atom or one represents a hydrogen atom and the other represents an alkylsulfonyl group or an acyl group. X and Z each represent a group that can be substituted on a benzene ring, n is 1 to 4, l is 0 to 4
And when n and l are 2 or more, X and Z may be the same or different, and may form a ring. Y
And L represent a divalent linking group. However,-(OCH ₂ C
H ₂ )-is excluded. m represents 0 to 5.

Hereinafter, specific examples of the hydrazine compound preferably used in the present invention are shown below, but the present invention is not limited to these.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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Specific examples of other preferred hydrazine derivatives include, for example, US Pat. No. 5,229,24.
No. 8, No. 4 column to No. 60 column (1)
To (252).

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
No. 229,248, column 59 to column 80, can be synthesized by the method as described.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
^-1 mol, preferably 10 ^-5 to 10 ^-2 mol.

The hydrazine derivative preferably used in the present invention is added to a silver halide emulsion layer and / or a layer adjacent thereto. The hydrazine compound used in the present invention can be used in any layer as long as it is on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. Molar ranges are preferred,
Particularly, the range of 10 ^-5 to 10 ^-2 mol is preferable.

(Promotion of nucleation) In the present invention, a nucleation promoter represented by the above-mentioned general formula [Na], [Nb] or [Nc] is used in order to effectively promote the contrast enhancement by the hydrazine compound. Is preferred.

In the general formula [Na], R ₁ , R ₂ ,
R ₃ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ₁ , R ₂ and R ₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorbing group in the molecule.

Specific examples of the general formula [Na] are shown below.

[0080]

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[0081]

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[0082]

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[0083]

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Next, in the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₄ may be connected to each other by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

The specific examples of the general formula [Nb] are shown below.

[0086]

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[0087]

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Next, in the general formula [Nc], Q is N
Or R represents a P atom, and R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substitutable group. L represents an m-valent organic group. R ₅ ~
R ₇ and L may have a plurality of groups bonded to each other to form a ring. m represents an integer of 1 to 5. X ^n- represents an n-valent anion, and n represents an integer of 1 to 5. X ^n- is L
May be connected. Specific examples of the displaceable group represented by R _{5 to} R ₇ include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), Cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl groups (eg, benzyl group, 2-phenethyl group, etc.), aryl groups (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.),
Alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (Eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group) , 3,
3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group) Group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, I De group (e.g. phthalimido group), a Hajime Tamaki (e.g., pyridyl, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group). These groups may be further substituted with the groups described above. Examples of the group represented by L alkylene besides the above groups, arylene, -SO ₂ -, - SO
-, - O -, - S -, - N (R 8) - (R 8 is a hydrogen atom,
M represents an alkyl group or an aryl group) alone or in combination. m is preferably 1 or 2, and particularly preferably 2. Q is P
When it is an atom, R _{5 to} R ₇ are preferably an aryl group, particularly preferably a phenyl group.

L is preferably a phenyl group or an alkylene group. When Q is an N atom, R _{5 to} R ₇ and L are preferably a group in which a plurality of groups are bonded to each other to form a ring, and the formed ring is preferably a pyridine ring. Examples of the anion represented by X include chloride ion, bromine ion, iodine ion, acetate ion, oxalate ion, fumarate ion, benzoate ion, toluene sulfonate ion, methane sulfonate ion, benzene sulfonate ion, sulfate ion, and perchloric acid. Ions, carbonate ions, nitrate ions and the like. Hereinafter, specific examples of the compound of the general formula [Nc] will be described.

[0090]

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[0091]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258751.
No. 51 (3-1) to (3-6).

The nucleation accelerator used in the present invention can be used in any layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. . The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol. A plurality of nucleation accelerators may be used in the same layer or in different layers.

A redox compound can be used in the silver halide photographic light-sensitive material of the present invention. Hereinafter, the redox compound that can be used in the present invention will be described.

The redox compound has, as a redox group, hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones, α-aminoketones and the like.

Preferred redox compounds are compounds having a —NHNH— group as a redox group and compounds represented by the following general formulas [2], [3], [4], [5], [6] or [7]. is there.

[0097]

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[0098]

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Compounds having a -NHNH- group as a redox group include compounds represented by the following general formula [RE-a] or [RE-
b].

General formula [RE-a] T-NHNHC0V- (Time) -PUG General formula [RE-b] T-NHNHCOCOV- (Time) -PUG In general formulas [RE-a] and [RE-b], T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group. The aryl group represented by T and V includes, for example, a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. As a preferable substituent, a linear or branched alkyl group ( Preferably those having 2 to 20 carbon atoms, such as methyl, ethyl, isopropyl, dodecyl and the like; alkoxy groups (preferably those having 2 to 21 carbon atoms such as methoxy, ethoxy and the like);
An aliphatic acylamino group (preferably having an alkyl group having 2 to 21 carbon atoms, such as an acetylamino group and a heptylamino group), an aromatic acylamino group, and the like;
These other, for example, a substituted or unsubstituted aromatic rings, such as described above -CONH -, - O -, - SO 2 NH -, - NH
CONH -, - including those attached with a linking group such as CH ₂ CHN-.

PUG includes 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, -Nitroimidazole and the like. These development inhibiting compounds are T-NH
Directly at the CO site of NH—CO— through a heteroatom such as N or S, or alkylene, phenylene, aralkylene,
It can be further connected via an N or S heteroatom via an aryl group. In addition, those obtained by introducing a development inhibiting group such as triazole, indazole, imidazole, thiazole, and thiadiazole into a hydroquinone compound having a ballast group can also be used.

For example, 2- (dodecylethylene oxidethiopropionamide) -5- (5-nitroindazol-2-yl) hydroquinone, 2- (stearylamido) -5- (1-phenyltetrazole-5-thio)
Hydroquinone, 2- (2,4-di-t-amylphenoxypropionamide) -5- (5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-
5- (2-mercaptothiothiadiazole-5-thio)
Hydroquinone and the like can be mentioned.

These redox compounds are disclosed in US Pat.
No. 269,929 can be synthesized.

The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer.

The addition of the above redox compound includes alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, dimethylformamide,
It can be added after dissolving in esters such as dimethylsulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. Those hardly soluble in water or organic solvents can be arbitrarily dispersed from 0.01 to 6 μm in average particle diameter by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed. The amount of the redox compound added is preferably from 10 ^-6 mol to 10 ^-1 mol, more preferably from 10 ^-4 mol to 1 ^-1 mol, per mol of silver halide.
It is in the range of 0 ^-2 mol.

Among the compounds represented by the formula [RE-a] or [RE-b], particularly preferred compounds are shown below.

[0107]

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[0108]

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Specific examples of other preferred redox compounds are described in JP-A-4-245243, 236.
(8) Page “0053” to 250 (22) Page “0068”
R-1 to R-50.

Hereinafter, the redox compounds represented by the general formulas [2] to [7] will be described. General formula [2] ~
In [7], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom.

R _{5 to} R ₉ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r1, r2 and r3 represent a substituent capable of substituting on a benzene ring. X ₁ and X ₂ are O or NH
Represents Z ₁ represents an atom group necessary for constituting a 5- to 6-membered heterocyclic ring.

W represents N (R ₁₀ ) R ₁₁ or an OH group;
R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. COUP represents a coupler residue capable of causing a coupling reaction with an oxidized form of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. T
m represents a timing group. m ₁ and p ₁ is an integer of 0 to 3. q ₁ represents an integer of 0-4. n represents 0 or 1. PUG represents a development inhibitor.

The above general formulas [2] to [7] (hereinafter, in the formula)
In the above, the alkyl group, aryl group and heterocyclic group represented by R ₁ and R _{5 to} R ₁₁ are preferably a methyl group, p
-Methoxyphenyl group, pyridyl group and the like. R
₂ and acyl group represented by R _3, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group, preferably an acyl group among the aryloxy carbonyl group, carbamoyl Group, a cyano group.

The total number of carbon atoms in these groups is preferably 1 to 20. R _{1 to} R ₁₁ may further have a substituent, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group) Methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group) , Naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino Group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group Ethylthio group, butylthio group, etc.), an arylthio group (e.g., phenylthio group), a sulfonylamino group (e.g., methanesulfonylamino group, etc. benzenesulfonylamino group),
Ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.),
Sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.) An alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an acyl group (eg, Acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl group, nitro group, imide group (for example, phthalimido group, etc.),
Heterocyclic groups (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, etc.) are exemplified. The following can be mentioned as the coupler residue represented by COUP.

Examples of the cyan coupler residue include a phenol coupler and a naphthol coupler. Examples of the magenta coupler include a 5-pyrazolone coupler, a pyrazolone coupler, a cyanoacetylcoumarone coupler, an open-chain acylacetonitrile coupler, and an indazolone coupler.
Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. Non-colored coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.).
Further, among the coupler residues represented by COUP, those preferably used in the present invention are represented by the following general formula (Coup)
-1) to general formula (Coup-8).

[0116]

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In the formula, R ₁₆ represents an acylamide group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0118]

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In the formula, R ₁₈ and R ₁₉ represent a halogen atom, an acylamide group, an alkoxycarbonylamide group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ each represent an aliphatic group. Represents an aromatic group, an aromatic group or a heterocyclic group. One of R ₂₀ and R ₂₁ may be a hydrogen atom. a is an integer of 1 to 4, b
Represents an integer of 0 to 5. When a and b are plural, R ₁₈ may be the same or different, and R ₁₉ may be the same or different.

[0120]

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In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0122]

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In the formula, R ₂₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₂₆ represents a hydrogen atom, a halogen atom, or a nitro group.

[0124]

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R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

5 to 6 represented by Z ₁ in the general formula [2]
The membered heterocyclic ring may be a single ring or a condensed ring;
5 to 6 having at least one of S and N atoms in the ring
Membered heterocycles. These rings may have a substituent, and specific examples include the aforementioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,40.
9,323 or 3,674,478, Res
erch Disclosure 21228 (198
(December, 1st year), or JP-A-57-56837, JP-A-4-438 and the like.

Preferred development inhibitors as PUG are described, for example, in US Pat. No. 4,477,563 and JP-A-60-21.
No. 8644, No. 60-221750, No. 60-233
650 or 61-11743.

Hereinafter, the general formulas [1] to
Specific examples of the compound represented by [6] are listed, but the present invention is not limited thereto.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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The general formula [2] preferably used in the present invention
The compounds represented by the formulas (1) to (7) are preferably contained in an amount of from 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, particularly from 1 × 10 ^-4 mol to 2 × 10 ^-2 mol, per mol of silver halide. Is preferred.

The compounds represented by the general formulas [2] to [7] may be used by dissolving them in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like. Can be. Further, it can be added as an emulsified dispersion using a known oil. Furthermore, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves by a method known as a solid dispersion method.

In the present invention, the redox compound may be present in a silver halide emulsion layer, in a layer adjacent to the emulsion layer, in another layer via the adjacent layer, and the like. Particularly preferably,
An emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer. Most preferably, a hydrophilic colloid layer is provided between the emulsion layer and the emulsion layer closest to the support, and the hydrophilic colloid layer is added to the hydrophilic colloid layer. Further, the redox compound may be contained in a plurality of different layers.

In the silver halide photographic light-sensitive material of the present invention, a dye dispersed in solid fine particles can be used.

As the solid-dispersed dye that can be used, compounds represented by the following general formulas [8] to [13] are preferably used.

[0143]

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In the formula, A and A 'may be the same or different and each represents an acidic nucleus, B represents a base, Q represents an aryl group or a heterocyclic group, Q' represents a heterocyclic group,
X ₄ and Y ₁ may be the same or different and each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m ₂ represents 0 or 1, t represents 0, 1 or 2, and p ₂ represents 0 or 1. However, the general formula [8]
~ The dye represented by [13], a carboxy group in the molecule,
It has at least one group selected from a sulfonamide group and a sulfamoyl group.

The general formula [8],

The acidic nucleus represented by A and A 'in [9] and [10] is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione. , Pyrazolidinedione, oxazolidinedione, hydroxypyridone,
Pyrazolopyridone.

The basic nucleus represented by B in the general formulas [10] and [12] is preferably pyridine, quinoline,
Oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in formulas [8] and [11] include a phenyl group and a naphthyl group. The general formulas [8], [11] and [1]
Examples of the heterocyclic group represented by Q and Q ′ in 3) include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group, and a thienyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include, for example, a substituent such as an amino group or a heterocyclic group in the compounds of the aforementioned general formulas [8] to [12]. These substituents may be used in combination of two or more. Preferred substituents include alkyl groups having 1 to 8 carbon atoms (e.g., methyl, ethyl, t-butyl, octyl, 2-hydroxyethyl, 2-methoxyethyl, etc.), hydroxy, cyano, Halogen atom,
(Eg, a fluorine atom, a chlorine atom, etc.), an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a methylenedioxy group, a butoxy group, etc.), a substituted amino group (eg, a dimethylamino group) , Diethylamino group, di (n-butyl) amino group, N-ethyl-
N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc., carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.) And a sulfamoyl group (for example, a sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, etc.), and these substituents may be combined.

X ₄ and Y _{1 in the} general formulas [11] and [12]
The electron-withdrawing groups represented by may be the same or different, and the σp value of the substituent constant Hammett (edited by Toshio Fujita,
"Structure-Activity Relationship of Drug No. 122, Special Edition of Chemistry,"
Pp. 103 (1979) in Nankodo and the like. ) Is preferably 0.3 or more, for example, a cyano group,
Alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethyl Carbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidocarbonyl group, etc.), alkylsulfonyl group ( For example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, 4-chloro Sulfonyl group, etc.).

L ₁ , L ₂ and L in the general formulas [8] to [12]
_The methine group represented by ₃ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (such as a methyl group, an ethyl group, and a hexyl group), an aryl group (such as a phenyl group, a tolyl group, and a -hydroxyphenyl group), and an aralkyl group (such as a benzyl group). , A phenethyl group, etc.), a heterocyclic group (eg, a pyridyl group, a furyl group, a thienyl group, etc.), a substituted amino group (eg, a dimethylamino group,
A diethylamino group, an anilino group, etc.) and an alkylthio group (eg, a methylthio group).

Among the dyes represented by the general formulas [8] to [13], those having at least one carboxyl group in the molecule are preferably used, and more preferably the general formula [8]
And particularly preferably a dye in which Q in the general formula [8] is a furyl group. Specific examples of preferably used dyes are shown below.

[0151]

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[0152]

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[0153]

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Other preferred specific examples of the compounds represented by the general formulas [8] to [13] include, for example, Japanese Patent Application No. 5-2.
No. 77011, pages 19-30. I-1 to N
o. I-30, II-1 to II-12, III-1 to III-8,
Examples include, but are not limited to, IV-1 to IV-9, V-1 to V-8, and VI-1 to VI-5.

A method for producing a solid fine particle dispersion of a dye is described in JP-A-52-92716 and JP-A-55-15553.
No. 50, No. 55-155351, No. 63-19794
No. 3 and No. 3-182743, world patent WO88 / 0
The method described in No. 4794 or the like can be used.
Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound to be dispersed in solid fine particles is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, dissolve the compound in a weakly alkaline aqueous solution and then lower the pH to make it weakly acidic. A method of precipitating fine solid particles or a weakly alkaline solution of the compound and an aqueous acidic solution, pH
A dispersion of the compound can be obtained by a method in which the particles are mixed at the same time while adjusting the particle size to produce a particulate solid.

The solid fine particle dispersion may be used alone, or two or more kinds may be used as a mixture, or may be used as a mixture with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously. When producing a solid fine particle dispersion in the presence of an aqueous dispersion medium,
During or after dispersion, a surfactant is preferably co-present.

As such a surfactant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. Alkyl benzene sulfonate, alkyl naphthalene sulfonate,
Alkyl sulfates, sulfosuccinates,
Anionic surfactants such as sulfoalkylpolyoxyethylene alkylphenyl ethers and N-acyl-N-alkyltaurines and nonionic surfactants such as saponins, alkylene oxide derivatives and alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, for example, compounds of Nos. 1 to 32 described on pages 32 to 46 of Japanese Patent Application No. 5-277011, but are not limited thereto. The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the dispersion conditions of the dye, but is usually preferably from 0.1 to 2000 mg per g of the dye, more preferably. May be 0.5 to 1000 mg, particularly preferably 1 to 50 mg.
0 mg may be sufficient.

The concentration of the dye in the dispersion is 0.01
使用 50% by weight is preferably used,
More preferably, it is 0.1 to 30% by weight. The addition position of the surfactant is preferably added before the start of dispersion of the dye,
If necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone, respectively, or two or more kinds may be combined, or both activators may be combined.

The solid fine particle dispersion has an average particle diameter of 0.01.
It is preferable that the particles be dispersed so as to have a thickness of from 0.1 to 5 μm, more preferably from 0.01 to 1 μm, particularly preferably from 0.1 to 1 μm.
01 to 0.5 μm.

The dispersion coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 A hydrophilic colloid used as a binder for a photographic component layer can be added to the solid fine particle dispersion before or after the start of dispersion. . As the hydrophilic colloid, it is advantageous to use gelatin.In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, and gelatin having a polymerizable ethylene group-containing monomer. Graft polymer, carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate,
Synthetic hydrophilic polymers such as polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein, etc. Can be used. These may be used in combination of two or more. The amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is 0.1 to 12% by weight.
It is preferable to add so as to obtain the following, more preferably 0.5 to 8%.

The solid fine particle dispersion is composed of layers constituting a photographic material, for example, a silver halide emulsion layer, an upper emulsion layer, a lower emulsion layer,
It can also be used as a layer such as a protective layer, a support undercoat layer, and a backing layer. In particular, in order to enhance the antihalation effect, it is preferably added to a layer between the support and the emulsion layer or a constituent layer opposite to the emulsion layer. In order to particularly enhance the effect of improving the safelight property, it is preferable to add the compound to the layer above the emulsion layer.

The preferable use amount of the solid fine particle dispersion of the dye is not uniform depending on the kind of the dye and the characteristics of the photographic material, but is preferably 1 mg to 1 g per 1 m ^{2 of} the photographic material, and more preferably 5 mg / m ^2. ~ 800 mg,
Particularly preferably, it is 10 to 500 mg.

In the present invention, between the photosensitive emulsion layer and the support,
It may have a photosensitive emulsion layer containing a dye dispersed in a solid state, other photosensitive and non-photosensitive emulsion layers,
The non-emulsion layer (hydrophilic colloid layer, hydrophobic polymer layer) can also contain a solid dispersed dye. It may be contained in any layer on the side opposite to the emulsion layer with respect to the support. Further, any layer may have a water-soluble dye. The addition amount of the dye dispersed in a solid state in the present invention is preferably an amount capable of obtaining an absorbance of 0.001 to 2.0 in at least a part of a wavelength region of a light source used for exposure, and particularly preferably. The above absorbance is 0.005 to 1.
5 is added. In the present invention, a dye having another absorption wavelength can be used in any layer.

The light-sensitive material of the present invention is most effective when used as an output light-sensitive material.
A laser, a HeNe laser, a red laser diode, an infrared semiconductor laser, and a red LED laser are typical, but any other laser such as a blue laser such as a HeCd laser can be used. The effects of the present invention are not limited to laser output light-sensitive materials, but are also effective in applications such as shooting light-sensitive materials and return light-sensitive materials.

In the silver halide photographic light-sensitive material of the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization may be appropriately selected and used in combination.

The chemical sensitization may not be performed. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanines, polysulfide compounds and the like can be used in addition to the sulfur compounds contained in gelatin.

As the selenium sensitizer, triphenylselenophosphine and the like are preferably used. A wide variety of selenium compounds can be used as the selenium sensitizer.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N
-Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (triphenylphosphine selenide,
Diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 ° C, more preferably 45 to 90 ° C.
The temperature is not less than 80 ° C and not less than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

As a method for adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are hardly soluble in water, various methods can be adopted. For example, there is a method in which a sulfur sensitizer and / or a selenium sensitizer and / or a tellurium sensitizer are sufficiently mixed in advance with a gelatin solution and then added. Alternatively, a method of dissolving in a low-boiling organic solvent in which a sensitizer is dissolved and then emulsifying and dispersing in the presence of a surfactant to add the sensitizer can also be adopted.
In this method, it is preferable to remove the low-boiling organic solvent after emulsification and dispersion. Further, a method disclosed in Japanese Patent Application Laid-Open No. 4-140739 is also possible in which the compound is added in the form of an emulsified dispersion of a mixed solution with a water-insoluble and organic solvent-soluble polymer. Also, a method of arbitrarily dispersing the average particle diameter from 0.01 to 6 μm by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like can be adopted. The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

As the reduction sensitizer, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

Oxidizing Agent In the present invention, an oxidizing agent for silver can be used in the production process of the photosensitive material. The oxidizing agent usable in the present invention, for example, as inorganic oxidizing agent, hydrogen peroxide (water), adducts of hydrogen peroxide (e.g., _{NaBO 2 · H 2 0 2 ·} 3H 2 O,
_{2NaCO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ .H ₂ O ₂ .2H ₂ O, etc., peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₄ P ₂ O ₈ ), peroxy complex compounds (eg, K ₂ [Ti (O ₂ ) C ₂ O ₄ ]
· 3H ₂ O, 4K ₂ SO ₄ · Ti (O ₂ ) · OH · SO ₄ ·
2H ₂ O, Na ₂ [VO (O ₂ ) (C ₂ O ₄ ) ₂ ] · 6H ₂ O
Oxyacids such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO), halogen elements such as iodine and bromine, and perhalates (eg, potassium periodate) , High valent metal salts (such as potassium ferricyanide) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T, chloramine). B, etc.). Particularly preferred oxidants are ozone,
Hydrogen peroxide and its adducts, inorganic oxidants of halogen elements, quinones and organic oxidants that release active halogens.

The amount of the oxidizing agent added to silver used in the present invention is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide. More preferably, 10 ^-6 to 10
^-2 mol, particularly preferably 10 ^-5 to 10 ^-3 mol.

In order to add the oxidizing agent for silver used in the present invention during the chemical sensitization step, a method usually used when adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is prepared as an aqueous solution having an appropriate concentration, and a water-insoluble or hardly soluble compound is dissolved in a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, and amides. Can be dissolved in a solvent that does not adversely affect the photographic properties and can be added. Further, it can be added in a solid dispersion state.

The timing of adding the oxidizing agent to silver used in the present invention may be at any time in the production process of the amount of the silver halide sensitized material, but the preferred timing is to apply the silver halide grains from the preparation process to the coating on the support. This is the process up to just before.

In the present invention, the silver halide composition in the silver halide emulsion may be pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, or chloroiodide containing 60 mol% or more of silver chloride. Preferably, it is silver bromide. The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG.
K. Mees & T. H. By James: The the
ory of the photographic p
process, 3rd edition, 36-43 (1966 Mc
Millan).

The shape of the silver halide grains is not particularly limited, and may be any of a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedral shape, and any other shapes. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
So-called monodisperse emulsions containing 0%, preferably 95% are preferred.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are subjected to cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt in at least one of the steps of forming or growing the grains. It is preferable to add a complex salt containing an element from Groups 3 to 13 of the periodic table, such as an osmium salt, an iron salt, a copper salt, a platinum salt, and a palladium salt. As a ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used. The surface of the silver halide grains can be controlled in halogen composition by using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like. In the present invention, as the silver halide grains, particle size, sensitivity, crystal habit, photosensitive wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, desalting method and other production conditions, surface A plurality of types of particles having different states, chemically sensitized states, and the like can be used in combination. In that case,
These silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

The silver halide emulsion and its preparation method are described in detail in RD17643, pp. 22-23 (197)
(December 2008) or in the literature cited.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength by using a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These pigments include:
As the basic heterocyclic nucleus, any nucleus commonly used for cyanine dyes can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, ie, indolenine nuclei , Benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms. In a merocyanine dye or a complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus,
5- to 6-membered heterocyclic rings such as thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

More specifically, RD17643 (Jan.
February issue) page 2, page 3, US Patent No. 4,425,425
And No. 4,425,426. Sensitizing dyes are disclosed in U.S. Pat.
The dissolution may be carried out using ultrasonic vibration described in U.S. Pat. Other methods for dissolving or dispersing the sensitizing dye of the present invention in an emulsion include those described in U.S. Pat. Nos. 3,482,981, 3,585,195 and 3,469,987. No. 3,425,835,
No. 3,342,605, British Patent No. 1,271,3
No. 29, No. 1,038,029, No. 1,121,
No. 174, U.S. Pat.
No. 658,546 can be used.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. A useful combination of a dye exhibiting supersensitization and a substance exhibiting supersensitization are RD
17643 (published December 1978), page 23, IV, paragraph J.

The light-sensitive material used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-
Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3). 3a, 7-tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like Can be added. Particularly preferred are a substituted or unsubstituted heterocyclic or fused heterocyclic ring containing any of N, O, S and Se, and a water-soluble halide.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalic acids (mucochloric acid, phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin , Isocyan Over preparative acids, the carboxyl group activated hardeners, etc., may be used alone or in combination.

The photosensitive emulsion layer and / or non-photosensitive hydrophilic colloid layer of the present invention may contain various additives for various purposes such as coating aids, antistatic, improvement of slipperiness, emulsification dispersion, prevention of adhesion and improvement of photographic properties. May be used.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As gelatin, acid-processed gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, an amide group and the like, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, an —NR group. ₁ NR ₂ -R ₃ (R ₁ , R ₂ and R ₃ may be different from each other, a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group,
Carbamoyl group, amino group, sulfonyl group, sulfoxy group, iminomethylene group, alkenyl group, alkynyl group,
An arbitrary group bonded through an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, etc.), a cation group, or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, development accelerators, oils and the like can be mentioned.

With respect to these additives and the above-mentioned additives, specifically, RD17643 (supra), 22 to 31
What is described on a page etc. can be used.

The silver halide photographic light-sensitive material of the present invention has a layer structure composed of at least two layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween. Further, it may have a non-photosensitive emulsion. As the non-emulsion layer, any number of layers may be provided as necessary between the support and the emulsion layer closest to the support, between a plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be. In these layers, a state in which a water-soluble or water-insoluble dye, an imagewise or non-imagewise development adjusting (suppression or acceleration) agent, a contrasting agent, a physical property adjusting agent, etc. are dissolved in an aqueous solution or an organic solvent, Alternatively, it can be contained in a form dispersed in solid fine particles (which may or may not be protected by oil). The emulsion layer may be one side or both sides with respect to the support. Even on one side, an arbitrary number of hydrophilic or non-hydrophilic layers can be provided in combination on the opposite side. In particular, when a layer of a hydrophobic polymer is provided outside the hydrophilic colloid layer with respect to the support, the drying property can be improved.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate synthetic polymers (which may contain colored content), or polyethylene or polyethylene. A paper support coated with a polymer such as terephthalate; These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

As the developing agent which can be used in the image forming method of the silver halide photographic material of the present invention, dihydroxybenzenes (for example, hydroquinone,
Chlorhydroquinone, bromohydroquinone, 2,3
-Dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-)
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-
Pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-amino) Phenol, N-methyl-p-aminophenol, 2,4
-Diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazoline, etc.), transition metal complex salts (Ti, V, C
A complex salt of a transition metal such as r, Mn, Fe, Co, Ni, Cu, etc. These may be in any form having a reducing power in order to be used as a developer. For example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , F
e2 ^{+ and the} like, and as ligands, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof;
Phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and salts thereof).

The developer used in the method for processing a silver halide photographic light-sensitive material of the present invention may not substantially contain a dihydroxybenzene compound. in this case,
It is preferable to contain a compound represented by the following general formula (A).

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In the general formula (A), R ₁ and R ₂ are each
Independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group,
R ₁ and R ₂ may combine with each other to form a ring. k is 0
Or 1 and when k is 1, X is -CO- or -CS-
Represents a group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

In the compound represented by the above general formula (A), R ₁ and R ₂ are bonded to each other to form a ring.
The compound represented by (Aa) is preferred.

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In the above formula (Aa), R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group , A sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁ represents O or S,
Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Examples of the substituent of the alkyl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An aryl group having 6 to 20 carbon atoms (e.g., phenyl, naphthyl, etc.), a heterocyclic group (e.g., 2,2,6,6-tetramethylpiperidyl, quinolizinyl, N, N'-diethylpyrazolidinyl, Pyridyl group), having 1 to 20 carbon atoms
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), Heterocyclic oxy group (for example, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (for example, acetylamino, heptylamino, propionylamino group, etc.), amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.) )
And the like.

Examples of the substituent of the amino group include a halogen atom (for example, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group, etc.), Alkyl groups such as methyl, ethyl, butyl, cyclohexyl, isopropyl,
Dodecyl group, etc.), heterocyclic group (for example, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-
Diethylpyrazolidinyl group, pyridyl group, etc.), carbon number 1
An alkoxy group (e.g., methoxy, ethoxy group, etc.), an aryloxy group (e.g., phenoxy group) having 6-20 carbon atoms, an alkenyloxy group (e.g., allyloxy group, etc.) having 1-20 carbon atoms, 20 alkynyloxy groups (such as propargyloxy group), heterocyclic oxy groups (such as pyridyloxy group), and having 1 to 20 carbon atoms
(For example, acetyl group, heptyl group, propionyl group, etc.).

Examples of the substituent of the alkylthio group include a halogen atom (for example, Cl, Br and the like), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (for example, a phenyl group and a naphthyl group), and a heterocyclic group (for example, 2,2,6,6
-Tetramethylpiperidyl group, quinolizinyl group, N,
N'-diethylpyrazolidinyl group, pyridyl group, etc.), an alkoxy group having 1 to 20 carbon atoms (eg, methoxy group, ethoxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group, etc.), carbon An alkenyloxy group having 1 to 20 carbon atoms (for example, allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (for example, propargyloxy group), a heterocyclic oxy group (for example, pyridyloxy group),
And 26 amino groups (eg, acetylamino group, heptylamino group, propionylamino group, etc.) and amino groups (eg, amino, methylamino, dimethylamino, dibenzylamino group, etc.).

Examples of the substituent of the aryl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
Butyl, cyclohexyl, isopropyl, dodecyl group, etc.), heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), carbon An alkoxy group having 1 to 20 carbon atoms (such as a methoxy group or an ethoxy group), an aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), An alkynyloxy group having 1 to 20 atoms (eg, propargyloxy group), a heterocyclic oxy group (eg, pyridyloxy group), an acylamino group having 1 to 26 carbon atoms (eg, acetylamino, heptylamino, propionylamino group, etc.); Amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.)
And the like.

Examples of the substituent of the above alkoxy group include:
A halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group,
A C1-C20 alkyl group (e.g., methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl, etc.), a heterocyclic group (e.g., 2,
2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc., aryloxy group having 6 to 20 carbon atoms (for example, phenoxy group, etc.), carbon number of 1 Alkenyloxy group (e.g., allyloxy group) having 1 to 20 carbon atoms, alkynyloxy group (e.g., propargyloxy group) having 1 to 20 carbon atoms, heterocyclic oxy group (e.g., pyridyloxy group), and 1 to 26 carbon atoms.
(E.g., acetylamino group, heptylamino group, propionylamino group, etc.) and amino group (amino, methylamino, dimethylamino, dibenzylamino group, etc.).

Examples of the substituent of the sulfo group, carboxyl group, amide group, and sulfonamide group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an alkali metal group (eg, sodium, potassium, etc.), 6
To 20 aryl groups (eg, phenyl group, naphthyl group, etc.), alkyl groups having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc.), and heterocyclic groups (eg, 2, 2, 6) , 6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), having 1 to 20 carbon atoms
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), Heterocyclic oxy group (eg, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (eg, acetylamino, heptylamino, propionylamino group, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino group, etc.) And the like.

Next, the formula (A) or the formula (A-
Examples of the compound represented by a) are shown below, but the present invention is not limited thereto.

Formula (A)

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[0211]

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Formula (Aa)

[0213]

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[0214]

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[0215]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the image forming method of the silver halide photographic light-sensitive material of the present invention, development substantially free of hydroquinones (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc.) is carried out. Liquid can be used. The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer.

The developing agents described above can be used alone or in combination. For example, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes, or 3-
A combination of pyrazolidones and ascorbic acid, a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts can be used. The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / l.

In the present invention, silver sludge inhibitors are disclosed in JP-B-62-4702 and JP-A-3-51844.
4-26838, 4-362942, 1-3
19031 and the like.

Further, the developing waste liquid can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

Examples of the sulfite and metabisulfite used as a preservative in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l.

[0222]

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of silver halide emulsion A1)
70 mol% of silver bromide, balance of silver bromide having an average diameter of 0.0
9 μm silver chlorobromide core particles were prepared. When core particles are mixed
To K_ThreeRh (N0)_Four(H _TwoO)_TwoIn particle form per mole of silver
7 × 10 per mol of silver at the end of formation^-8Mole, K_ThreeOs
Cl₆To 8 × 10^-6P at a temperature of 40 ° C. in the presence of molar addition
H3.0 while maintaining the silver potential (EAg) at 165 mV.
An aqueous silver acid solution and a water-soluble halide solution were simultaneously mixed.

EAg was added to the core particles with a salt solution of 125 m
V and shelled using a double jet method. At this time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ⁻⁷ per mole of silver.
And 9 × 10 ⁻⁸ mol of K ₃ RhCl ₆ . Further, KI conversion was performed using silver iodide fine particles, and the obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (average diameter: 0.14 μm) (silver chloride: 70 mol%,
(A silver iodobromide 0.2 mol%, the balance being silver bromide).

Then, the modified gelatin described in JP-A-2-280139 (Example in which the amino group in the gelatin is substituted with phenylcarbamyl and exemplified by compound G-8 on page 287 (3) of JP-A-2-280139) is used. Use desalted.
The EAg after desalting was 190 mv at 50 ° C. Potassium bromide was added to the resulting emulsion at 8.5 × 10 5 per mole of silver.
PH 5.6, EAg12 with addition of ^-4 mol and citric acid
After adjusting to 3 mv and adding 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) to cause a reaction, the inorganic sulfur (S
8) Compound (added after mixing a 0.01% methanol solution with an equal amount of water and crystallizing for 10 minutes, average particle size about 300)
nm) and 1.5 × 10 ^-5 mol of chloroauric acid, and chemically ripened at a temperature of 55 ° C. until the maximum sensitivity is obtained.
After cooling to 40 ° C., 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 −3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and potassium iodide was added in an amount of 5 ×.
After adding 10 ^-3 mol, the pH was adjusted to 5.1 with citric acid, and then 100 mg of sensitizing dye d-1 was added.

(Preparation of silver halide emulsion A2) K ₃ RhCl ₆ in the shell portion was added to silver halide emulsion A1 in an amount of 6 × 1.
A silver halide emulsion A2 was prepared in exactly the same manner except that the amount was ^0-8 mol. With the same chemical sensitization, the emulsion of A2 is 40% faster than the emulsion of A1.

(Preparation of a silver halide photographic light-sensitive material containing a hydrazine derivative for a printing plate-making scanner)
No. 241264 On a 100 μm thick transparent polyethylene terephthalate support having been subjected to the antistatic treatment described in Example 1, a gelatin subbing layer having the following formulation 1 was prepared so that the gelatin amount was 0.55 g / m ² . The silver halide emulsion layer 1 of Formulation 2 was further overlaid thereon with the silver halide emulsion layer 2 of Formulation 3 so that the silver amount was 1.73 g / m ² and the gelatin amount was 0.66 g / m ^2. silver amount 1.73 g / m ^2, so that the amount of gelatin is 0.66 g / m ^2, further below the amount of gelatin of the emulsion protective layer coating solution of the formulation 4 is 1.3 g / m ²
At the same time. On the other side of the undercoat layer, a backing layer of the following formulation 6 was coated with a gelatin amount of 2.3 g / g.
m ² , a backing protective layer of the following formula 7 was further coated on the emulsion layer side with a curtain coating method at a speed of 200 m / min so that the gelatin amount was 0.7 g / m ^2. After the simultaneous multi-layer coating and cooling setting, the backing layer side is simultaneously multi-layer coated and cooled and set at -1 ° C.
A sample was obtained by drying both sides simultaneously.

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.55 g / m ² Saponin 56.5 mg / m ² Solid disperse dye AD-8 10 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 10 mg / m ² Sterilization Agent Z 0.5 mg / m ² Prescription 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A1 1.73 g / m ² equivalent of silver amount Hydrazine compound H-1 2 × 10 ⁻³ mol / mol Ag Compound a 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex L1 (particle size 0.25 μm) 0.25 g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyrimidine 1 mg / m ² gallate n- propyl ester 25 mg / m ² of ascorbic acid 20mg / m ² EDTA 25mg / Sodium 15 mg / m ² coating solution pH ² polystyrene sulfonic acid was 5.2.

Formulation 3 (Composition of Silver Halide Emulsion Layer 2) Silver Halide Emulsion A2 Amount of silver equivalent to 1.73 g / m ² Hydrazine compound H-25 4 × 10 ⁻³ mol / Agl mol Nucleation accelerator (exemplary) Nc-14) 7 mg / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 4 × 10 ⁻³ mol / Agl mol Saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / M ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 25 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Dye f5 15 mg / m ² Polymer latex L2 0.25 g / m ² Colloidal silica ( Average particle size: 0.05 μm) 150 mg / m ² dextrin compound (Towa Kasei; PO-20) 0.3 g / m ² gelatin is phthalated gelatin The pH of the coating solution was 4.
It was 8.

Formulation 4 (Emulsion protective layer composition 1) Gelatin 0.6 g / m ² Surfactant S1 20 mg / m ² Compound a 50 mg / m ² Polymer latex L3 (average particle size 0.1 μm) 0.25 g / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² Formulation 5 (Emulsion protective layer composition 2) Gelatin 0.7 g / m ² Nucleation promoter (AM-1) 14 mg / m ² Inorganic matting agent ( Amorphous silica having an average particle size of 4.0 μm manufactured by Fuji Devison Co., Ltd. Amount shown in Table 1 Organic matting agent (monodispersed polymethyl methacrylate having an average particle size of 2.8 μm) Amount shown in Table 1 (The organic matting agent is naphthalenesulfonic acid) Was used as a gelatin dispersion with the surfactant as an activator, but the amounts in the table are the amounts added as polymer particle components.) Surfactant S1 20 mg / m ² Redox compound R1 30 mg / m ² Compound a 30 mg / m ² Polymer latex L3 (average particle size 0.1 μm) 0.25 g / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² Redox compound R1 30 mg / m ² Hardener h2 80 mg / m ² Hardener 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ^{2 The} redox compound was dispersed by the following dispersion method. Used.

(Method of Dispersing Redox Compound) Redox compound 2 g Ethyl acetate 80 g The redox compound is dissolved according to the above formulation, and mixed with the following gelatin solution.

6 g of 10% TK-AX (manufactured by Takemoto Yushi Co., Ltd.) 180 g of 15% aqueous gelatin 180 g of a mixed solution was preliminarily dispersed at 40 ° C. with a homogenizer for 5 minutes, and then the dispersion was put into the main dispersion and the pressure was reduced to 130 mmHg to remove ethyl acetate. I do. Make up to 280g with water.

Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Polymer latex L4 0.3 g / m ² colloidal silica (average particle size 0 .05μm) 100mg / sodium m ² of polystyrene sulphonic acid 10 mg / m ² dye f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² hardener h3 100 mg / M ² Zinc hydroxide 50 mg / m ² Compound D 10 mg / m ² EDTA 50 mg / m ² Formulation 7 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethyl methacrylate 50 mg / m with an average particle size of 5 μm m ² average particle size 3 μm irregular silica 12.5 mg / m ² sodium-di- (2-ethyl Lehexyl) -sulfosuccinate 10 mg / m ² Surfactant S1 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Dye SF-2 (solid dispersion) 20 mg / m ² Compound a 50 mg / m ² Hardener h2 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² (The solid-dispersed dye was prepared by dissolving the exemplified dye SF-2 in an alkali, and then adding citric acid in an amount equal to 1.2 times the acid group. The other dyes (including those from Example 2 onwards) were Zr
It was dispersed with O beads to obtain a powder dispersion having a particle size of 0.1 μm.

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[0237]

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[0238]

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[0239]

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(Developer Composition) Diethylenetriamine pentaacetic acid / pentasodium salt 1 g per liter of working solution 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g erythorbic acid 5 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxy Methyl-3-pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g KOH was added in an amount to make the pH of the working solution 10.4.

(Composition of fixing solution) Ammonium thiosulfate (70% aqueous solution) per liter of working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Sulfuric acid Aluminum (27% aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 4.9.

(Processing conditions) Automatic developing machine G manufactured by Konica Corporation
Development processing was performed using R-960 under the following conditions.

(Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 50 ° C. 30 seconds Total 100 seconds (Evaluation of sensitivity and gamma) Exposure was performed using 633 nm HeNe as a light source. 1.5 × 1 with laser sensitometer using laser
Step exposure was performed while changing the light amount in ^0-7 seconds, and processing was performed under the above-described developing conditions. The obtained developed sample is
It was measured with DA-65 (Konica Digital Densitometer). The sensitivity in the table is represented by the relative value of the reciprocal of the amount of light that gives a density of 2.5, The sensitivity of 1 is set to 100, and the larger the number, the higher the sensitivity. Gamma was evaluated by the amount of light giving a density of 0.1 and a density of 3.2 (the index of gamma is widely known in the art).

(Evaluation of Scratch Resistance)
The surface was rubbed with a stainless steel rod having a diameter of 5 mm, developed, and then subjected to a development process. The number of blackening flaws generated was evaluated in the following five steps. 5 shows no scratches and is excellent, and 2 or less shows that it is not practical. Table 1 shows the obtained results.

[0245]

[Table 1]

As is clear from the results in Table 1, the sample of the present invention has excellent scratch resistance without deteriorating sensitivity and gamma.

Example 2 Sample No. 1 of Example 1 In 18, a sample was prepared in which the hydrazine compound and the nucleation promoting agent in the protective layer were changed as shown in Table 2, and the same evaluation as in Example 1 was performed. Table 2 shows the obtained results.

[0248]

[Table 2]

From the results shown in Table 2, it can be seen that the sample according to the present invention containing the hydrazine compound or the hydrazine compound and the nucleation accelerator in the protective layer is superior in the relationship among sensitivity, gamma and scratches.

Example 3 Sample No. 1 of Example 1 The above W1 was used as a slipping agent in the composition of the emulsion protective layer 2 which was the uppermost layer for 1, 3, 8 and 18.
And colloidal silica (average particle size 0.05 μm) in Table 3
And the same evaluation as in Example 1 was performed. Table 3 shows the obtained results.

[0251]

[Table 3]

From the results shown in Table 3, it can be seen that the system in which the slipping agent and colloidal silica were added to the uppermost protective layer was superior in terms of sensitivity, gamma and abrasion resistance.

[0253]

According to the present invention, a silver halide photographic material having excellent abrasion resistance without deteriorating sensitivity and gamma and a processing method thereof can be obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/29 501 G03C 5/29 501

Claims (5)

[Claims] 1. A silver halide photographic material having a hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains a hydrazine compound, and Having at least two hydrophilic colloid layers in the outermost layer of the silver halide emulsion layer,
At least one of organic polymer particles having an average particle size of 1.0 to 10 μm and at least one of organic polymer particles having an average particle size of 1.0 to 100 μm as a matting agent in the outer hydrophilic colloid layer.
A silver halide photographic light-sensitive material comprising a matting agent comprising various kinds of inorganic particles and a polymer latex in an inner hydrophilic colloid layer. 2. A silver halide photographic material having at least one hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains a hydrazine compound and the following general formula [ Na], containing at least one compound represented by [Nb] or [Nc],
In addition, the outermost layer of the silver halide emulsion layer has at least two hydrophilic colloid layers, and the outer hydrophilic colloid layer contains at least an organic polymer particle having an average particle size of 1.0 to 10 μm as a matting agent. 1 type and average particle size 1.0 ~
A silver halide photographic material comprising a matting agent comprising at least one inorganic particle of 100 μm and a polymer latex in an inner hydrophilic colloid layer. Embedded image (In the general formula [Na], R ₁ , R ₂ and R ₃ represent a hydrogen atom,
Represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group, and R ₁ , R ₂ , and R ₃ may form a ring. In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₄ may be connected to each other by a linking group to form a ring. In the general formula [Nc], Q represents an N or P atom, and R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substitutable group. L represents an m-valent organic group. R _{5 to} R ₇ and L may have a plurality of groups bonded to each other to form a ring. m represents an integer of 1 to 5. X ^n-
Represents an n-valent anion, and n represents an integer of 1 to 5.
X ^n- may be linked to L. ) 3. The matting agent as an inorganic particle having an average particle size of 3
3. The silver halide photographic light-sensitive material according to claim 1, wherein the thickness is from 100 to 100 [mu] m. 4. The silver halide photographic material according to claim 1, wherein the hydrophilic colloid layer containing the silver halide emulsion layer contains colloidal silica. 5. The method according to claim 1, wherein the outermost layer of the silver halide emulsion layer contains at least one slip agent.
5. The silver halide photographic light-sensitive material according to any one of the above items 4.